WO2020045447A1 - Couche mince diélectrique, élément capacitif, et substrat de circuit électronique - Google Patents

Couche mince diélectrique, élément capacitif, et substrat de circuit électronique Download PDF

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WO2020045447A1
WO2020045447A1 PCT/JP2019/033545 JP2019033545W WO2020045447A1 WO 2020045447 A1 WO2020045447 A1 WO 2020045447A1 JP 2019033545 W JP2019033545 W JP 2019033545W WO 2020045447 A1 WO2020045447 A1 WO 2020045447A1
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thin film
dielectric thin
dielectric
film
examples
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PCT/JP2019/033545
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English (en)
Japanese (ja)
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久美子 山▲崎▼
和希子 佐藤
純一 山▲崎▼
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Tdk株式会社
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Priority to US17/269,698 priority Critical patent/US11999616B2/en
Priority to JP2020539510A priority patent/JP7351304B2/ja
Publication of WO2020045447A1 publication Critical patent/WO2020045447A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/586—Nitriding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H01G4/306—Stacked capacitors made by thin film techniques
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/182—Printed circuits structurally associated with non-printed electric components associated with components mounted in the printed circuit board, e.g. insert mounted components [IMC]
    • H05K1/185—Components encapsulated in the insulating substrate of the printed circuit or incorporated in internal layers of a multilayer circuit
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10015—Non-printed capacitor

Definitions

  • the present invention relates to a dielectric thin film, a capacitor, and an electronic circuit board.
  • Patent Literature 1 describes a dielectric composition in which an additive is added to barium titanate powder to introduce defects into the crystal lattice of barium titanate to improve the relative dielectric constant.
  • the present invention has been made in view of such circumstances, and has as its object to provide a dielectric thin film, a capacitor, and an electronic circuit board having a large relative dielectric constant at a low frequency and a small dielectric loss.
  • the dielectric thin film according to the present invention is a dielectric thin film having an ABON-type oxynitride,
  • the ABON type oxynitride is represented by a composition formula A a B b O o N n , (O + n) / a ⁇ 3.00 Is satisfied.
  • the dielectric thin film according to the present invention has the above characteristics, so that the dielectric constant can be increased and the dielectric loss can be reduced particularly at a low frequency of about 1 kHz.
  • the dielectric thin film according to the present invention may satisfy (o + n) / a ⁇ 2.95.
  • the dielectric thin film according to the present invention may satisfy n / a ⁇ 0.05.
  • A may be one or more elements selected from Sr, Ba, Ca, La, Nd, Na and K, and B may be selected from Ta, Nb, Ti and W. One or more elements may be used.
  • the crystal structure of the ABON-type oxynitride may be a non-perovskite structure.
  • a capacitive element according to the present invention has the above dielectric thin film.
  • An electronic circuit board according to the present invention has a thin film capacitor having the above-mentioned dielectric thin film.
  • FIG. 1 is a schematic view of a thin film capacitor according to one embodiment of the present invention.
  • 4 is a graph showing XRD measurement results of Examples 1 to 3 and Comparative Example 1.
  • 6 is a graph showing the relationship between the oxygen partial pressure during film formation and tan ⁇ . It is a schematic diagram of an electronic circuit board concerning one embodiment of the present invention.
  • FIG. 1 is a schematic view of a thin film capacitor having a dielectric thin film according to the present embodiment.
  • the thin film capacitor 1 shown in FIG. 1 is formed on a substrate 11 in the order of a first electrode 12 and a dielectric thin film 13, and includes a second electrode 14 on the surface of the dielectric thin film 13.
  • the material of the substrate 11 is not particularly limited, but using a single crystal Si substrate as the substrate 11 is excellent in availability and cost. When flexibility is important, a Ni foil can be used as a substrate.
  • the thickness of the first electrode 12 is preferably 0.01 to 10 ⁇ m.
  • the thickness of the second electrode 14 is preferably 0.01 to 10 ⁇ m.
  • the dielectric thin film 13 is a polycrystalline dielectric thin film having an ABON-type oxynitride.
  • the dielectric constant of the dielectric thin film at a frequency of about 1 kHz can be increased, and the dielectric loss (tan ⁇ ) can be reduced.
  • the dielectric thin film 13 is preferably a polycrystalline dielectric thin film, and is preferably a thin film of a type different from the epitaxial film. Whether the dielectric thin film 13 is a polycrystalline dielectric thin film and is a thin film of a type different from an epitaxial film can be confirmed by, for example, an XRD pattern.
  • the type of A and the type of B are arbitrary, the type is an ABO oxide having a perovskite structure, that is, an oxide having an ABO 3- type crystal structure.
  • A is preferably one or more elements selected from Sr, Ba, Ca, La, Nd, Na and K, and B is one or more elements selected from Ta, Nb, Ti and W. It is preferred that A is most preferably Sr, and B is most preferably Ta.
  • the composition of the ABON type oxynitride can be represented by the composition formula A a B b O o N n in atomic ratio.
  • a a B b O o N n in atomic ratio.
  • composition formula A a B b O o N n satisfies the (o + n) / a ⁇ 3.00.
  • the relative dielectric constant at a frequency of about 1 kHz can be improved.
  • n / a ⁇ 0.05 may be satisfied.
  • the method of measuring the composition of the ABON-type oxynitride contained in the dielectric thin film 13 is arbitrary. For example, it can be measured by a method such as X-ray photoelectron spectroscopy or impulse heating melting extraction method (infrared absorption method).
  • the composition of the ABON-type oxynitride on the surface of the dielectric thin film 13 may be different from the composition of the ABON-type oxynitride inside the dielectric thin film 13. Good.
  • the surface portion of the dielectric thin film 13 refers to a portion whose depth from the surface of the dielectric thin film 13 is 10 nm or less.
  • the inside of the dielectric thin film 13 refers to a portion whose depth from the surface of the dielectric thin film 13 is 30 nm or more.
  • the composition formula of the ABON-type oxynitride on the surface of the dielectric thin film is A a1 B b1 O o1 N n1 in atomic ratio.
  • (o1 + n1) / a1 ⁇ 2.95 be satisfied.
  • n1 / a1 ⁇ 0.500 may be satisfied.
  • the method of measuring the composition of the ABON-type oxynitride on the surface of the dielectric thin film is arbitrary. For example, it can be measured by a method such as X-ray photoelectron spectroscopy or impulse heating melting extraction method (infrared absorption method).
  • the thickness of the dielectric thin film 13 is arbitrary, but is preferably from 10 nm to 1 ⁇ m.
  • the crystal structure of the ABON-type oxynitride contained on the surface and / or inside of the dielectric thin film 13 is arbitrary, but is preferably a non-perovskite structure.
  • the non-perovskite structure With the non-perovskite structure, the relative dielectric constant at a frequency of about 1 kHz can be further improved.
  • the non-perovskite structure refers to a structure other than the perovskite structure. In ABON-type oxynitride, it refers to a crystal structure that is not an ABO 2 N-type structure.
  • a method of confirming whether the ABON-type oxynitride contained on the surface and / or inside of the dielectric thin film 13 has a perovskite structure or a non-perovskite structure is arbitrary. For example, by measuring the XRD pattern, it is possible to confirm whether the ABON-type oxynitride has a perovskite structure or a non-perovskite structure.
  • an electronic circuit board 100 includes an epoxy resin substrate 10, a resin layer 20 formed on the epoxy resin substrate 10, and a thin film capacitor provided on the resin layer 20. 1, an insulating coating layer 30 formed on the resin layer 20 on which the thin film capacitor 1 is installed, an electronic component 40 installed on the insulating coating layer 30, and connected to the thin film capacitor 1 or the electronic component 40.
  • the thin film capacitor 1 may be in a state where the substrate 11 is removed or in a state where the substrate 11 is not removed.
  • the type of the metal wiring 50 is not particularly limited. For example, Cu and the like can be mentioned.
  • the thin film capacitor 1 is embedded in the electronic circuit board 100.
  • vacuum deposition, sputtering, PLD (pulse laser deposition), MO-CVD (metal organic chemical vapor deposition), MOD (metal organic decomposition), sol-gel method, CSD (chemical solution deposition) are exemplified.
  • the raw material used at the time of film formation may contain minute impurities or subcomponents, but there is no particular problem as long as the amount does not significantly impair the performance of the thin film.
  • the dielectric thin film 13 according to the present embodiment may also contain minute impurities and subcomponents to such an extent that the performance is not significantly impaired.
  • a film forming method by the PLD method when a film is formed by a method such as a PLD method, a sputtering method and a CSD method, a thin film finally obtained tends to be a polycrystalline film.
  • a film forming method by the PLD method will be described.
  • an Si single crystal substrate is prepared as the substrate 11.
  • a film is formed on the Si single crystal substrate in the order of SiO 2 , TiO x , and Pt, and the first electrode 12 made of Pt is formed.
  • the method for forming the first electrode 12 is not particularly limited. For example, a sputtering method, a CVD method, or the like can be given.
  • a metal oxide thin film is formed on the first electrode 12 by the PLD method. Further, a region where a thin film is not partially formed may be formed by using a metal mask in order to expose a part of the first electrode 12 according to an application.
  • a target containing a constituent element (Sr and / or Ta) of a target polycrystalline dielectric thin film is set in a film formation chamber.
  • a pulse laser is irradiated on the surface of the target.
  • the surface of the target is instantaneously evaporated by the strong energy of the pulse laser.
  • an evaporant is deposited on the substrate arranged to face the target to form a metal oxide thin film.
  • the composition formula of the metal oxide thin film is SrTaO x.
  • the type of the target is not particularly limited, and a metal oxide sintered body containing a constituent element (Sr and / or Ta) of the polycrystalline dielectric thin film to be produced, a simple metal of the constituent element, an alloy of the constituent element, or the like may be used. it can.
  • the respective elements are distributed on average, but the distribution may be varied within a range that does not affect the quality of the obtained polycrystalline dielectric thin film.
  • the number of targets is not necessarily one, and a plurality of targets containing some of the constituent elements of the polycrystalline dielectric thin film can be prepared and used for film formation.
  • the shape of the target is not limited, and may be a shape suitable for a film forming apparatus to be used.
  • x of the obtained metal oxide thin film can be controlled by adjusting film forming conditions, for example, gas pressure of oxygen and the like.
  • film forming conditions for example, gas pressure of oxygen and the like.
  • oxygen partial pressure film formation oxygen partial pressure
  • x becomes smaller, and defects (sites containing nothing) in the crystal lattice increase.
  • the oxygen partial pressure (film formation oxygen partial pressure) in the atmosphere during film formation increases, x increases, and defects in the crystal lattice decrease.
  • a sintered body containing Sr 2 Ta 2 O 7 may be used as a target.
  • the film formation conditions for example, the gas pressure of oxygen and the like, the above-mentioned x finally obtained can be controlled.
  • the metal oxide of the metal oxide thin film preferably satisfies SrTaO x , where 3.2 ⁇ x ⁇ 3.8.
  • the substrate 11 it is preferable to heat the substrate 11 with an infrared laser during the film formation in order to crystallize the metal oxide thin film to be formed.
  • the heating temperature of the substrate 11 varies depending on the metal oxide thin film, the constituent elements and the composition of the substrate 11, and the like.
  • the film is formed by heating to 600 to 800 ° C.
  • nitrogen is introduced into at least the surface of the metal oxide thin film in the metal oxide thin film, and the dielectric thin film 13 of the present embodiment is formed. Can be obtained.
  • Nitrogen treatment may be performed by introducing nitrogen radicals during film formation.However, in order to control the amount of introduced nitrogen to be not excessive, the metal oxide thin film after film formation is irradiated with nitrogen radicals. It is easier and preferable to perform the nitriding treatment. In the case where the nitriding treatment is performed by irradiating the formed metal oxide thin film with nitrogen radicals, the nitrogen content inside the dielectric thin film 13 is larger than the nitrogen content on the surface of the dielectric thin film 13.
  • the inside of the dielectric thin film 13 is substantially uniform. Therefore, when the composition inside the dielectric thin film 13 is measured by a method such as X-ray photoelectron spectroscopy or impulse heating melting extraction (infrared absorption method), the composition is measured by setting one measurement point. The obtained composition may be used as the composition inside the dielectric thin film 13.
  • the composition of the surface of the dielectric thin film 13 is preferably measured at three or more measurement points and averaged.
  • the thin film capacitor 1 can be manufactured.
  • the material of the second electrode 14 is not particularly limited, and Ag, Au, Cu, or the like can be used. There is no particular limitation on the method of forming the second electrode 14. For example, it can be formed by a sputtering method.
  • the reason why the relative dielectric constant of the dielectric thin film 13 of the present embodiment is particularly improved at a frequency of about 1 kHz is considered as follows.
  • SrTaO x N y which is a typical ABON-type oxynitride, tends to have a larger crystal lattice as the N content (y) increases. This is considered to be due to the fact that the N atom is larger than the O atom when comparing the N atom and the O atom.
  • SrTaO x which is a typical ABO type oxide, has a tendency in which the crystal lattice becomes smaller as the O content (x) decreases, which has been obtained by the present inventors. This is considered to be due to the fact that O atoms are larger than defects when O atoms are compared with defects.
  • N is introduced into a metal oxide thin film made of SrTaO x .
  • the distortion of the crystal lattice after the introduction of N increases as x decreases, the number of defects increases, and the crystal lattice decreases. This is because, since N atoms are larger than defects or O atoms, the smaller the crystal lattice before introducing N, the greater the distortion of the crystal lattice after introducing N.
  • the relative dielectric constant of the polycrystalline dielectric thin film mainly comes from ionic polarization and space charge polarization.
  • the polarization due to N atoms and defects is polarization classified as space charge polarization.
  • the ionic polarization has a large effect at a high frequency of about 1 MHz.
  • the dielectric thin film 13 according to this embodiment has a large relative dielectric constant particularly at a low frequency of about 1 kHz, and has a small dielectric loss (tan ⁇ ).
  • the electronic circuit board 100 is manufactured by, for example, the following method, but the manufacturing method of the electronic circuit board 100 is not limited to the following method.
  • an uncured resin layer which is a precursor of the resin layer 20 is formed on the epoxy resin substrate 10.
  • the thin film capacitor 1 is mounted on the uncured resin layer such that the first electrode 11 of the thin film capacitor 1 faces the uncured resin layer.
  • the thin film capacitor 1 may be in a state where the substrate 11 has been removed or in a state where the substrate 11 has not been removed.
  • the insulating coating layer 30 is formed on the uncured resin layer on which the thin film capacitor 1 is mounted, and the thin film capacitor 1 is sandwiched between the epoxy resin substrate 10 and the insulating coating layer 30.
  • the uncured resin layer is thermally cured to form the resin layer 20, and the epoxy resin substrate 10 and the insulating coating layer 30 are pressed.
  • the method of crimping For example, there is a method using a hot press.
  • the electronic component 40 is mounted on the insulating coating layer 30. Thereby, the electronic circuit board 100 in which the thin film capacitor 1 is embedded is obtained.
  • the uncured resin layer is in an uncured state at room temperature, and may be formed of a B-stage epoxy resin having a property of being thermoset by heating.
  • the insulating coating layer 30 may be formed of a resin such as an epoxy resin, a Teflon (registered trademark) resin, or a polyimide resin.
  • the present invention is not limited to these embodiments at all, and it is a matter of course that the present invention can be implemented in various modes without departing from the gist of the present invention.
  • the thin film capacitor 1 in the electronic circuit board 100 may be mounted by surface mounting.
  • the capacitance element according to the present invention is an element using dielectric properties, and includes a capacitor, a thermistor, a filter, a diplexer, a resonator, an oscillator, an antenna, a piezoelectric element, a transistor, a ferroelectric memory, and the like.
  • the polycrystalline dielectric thin film according to the present embodiment is suitably used particularly for a capacitor element required to have a high relative dielectric constant at a frequency of about 1 kHz and a small dielectric loss.
  • Examples 1 to 4, Comparative Examples 1 to 5 First, SrCO 3 powder and Ta 2 O 5 powder were prepared as raw materials of a Sr 2 Ta 2 O 7 sintered body used as a film formation target. The SrCO 3 powder and the Ta 2 O 5 powder were weighed so that the Sr / Ta molar ratio was 1.
  • the SrCO 3 powder and the Ta 2 O 5 powder were mixed for 16 hours by a wet ball mill using an ethanol solvent to obtain a mixed slurry.
  • the mixed slurry was dried at 80 ° C. for 12 hours using a thermostatic drier to obtain a mixture.
  • the mixture was lightly crushed in a mortar and placed in a ceramic crucible. And it heat-processed at 1000 degreeC in air
  • the calcined product was mixed again for 16 hours in a wet ball mill using an ethanol solvent to obtain a calcined slurry.
  • the obtained calcined slurry was dried at 80 ° C. for 12 hours with a constant temperature drier to obtain a calcined mixture.
  • a polyvinyl alcohol solution was added as a binder to the calcined mixture and mixed to obtain a granulated product.
  • the addition amount of the polyvinyl alcohol solution was 0.6% by weight based on 100% by weight of the pulverized material.
  • the granulated product was formed into a cylindrical shape having a diameter of about 23 mm and a height of about 9 mm to obtain a molded product.
  • the molding method was CIP molding.
  • the molded product was fired in an air atmosphere at 1400 ° C. for 2 hours using an electric furnace to obtain a sintered product. Further, the upper and lower surfaces of the sintered product were mirror-polished to obtain a film-forming target having a height of 5 mm. In addition, it was confirmed that the relative density of the obtained film formation target was 96 to 98%.
  • the film-forming target obtained as described above was set in a film-forming apparatus, and a Si substrate was set so as to face the film-forming target.
  • a Si substrate a substrate having a Pt film as a first electrode on the surface was used.
  • a metal oxide thin film was formed to a thickness of 400 nm by the PLD method.
  • the oxygen partial pressure in the atmosphere at the time of film formation was changed for each Example and Comparative Example. Specifically, the film forming oxygen partial pressure was set to the magnitude shown in Table 1.
  • the temperature at the time of film formation was 700 ° C., and nitrogen was not introduced into the atmosphere at the stage of forming the metal oxide thin film.
  • Example 4 oxygen was not intentionally introduced into the atmosphere. However, due to the performance of the vacuum device, it is estimated that oxygen having a maximum of about 0.001 Pa exists in the atmosphere.
  • Examples 1 to 3 and Comparative Example 1 a radical nitriding treatment was performed by irradiating the surface of the metal oxide thin film with nitrogen radicals for 10 minutes to obtain a dielectric material having an ABON-type oxynitride. A thin film was obtained.
  • Example 3 The values of (o + n) / a, o / a and n / a inside the dielectric thin film were calculated from the values quantified by X-ray photoelectron spectroscopy. Further, the results are shown in Table 2.
  • Example 3 and Comparative Example 1 since a considerable amount of N was present at least on the surface of the dielectric thin film, the diffusion of N from the surface to the inside of the dielectric thin film caused It can be estimated that the content of N inside is 0.0001 mol% or more.
  • Comparative Examples 2 to 5 in which the radical nitriding treatment was not performed were metal oxide thin films having SrTaO x , the N content was less than 0.0001 mol%, and the relative dielectric constant or tan ⁇ was inferior to Examples 1 to 4. It became.
  • the relative dielectric constant of each of the dielectric thin films of Examples 1 to 4 and Comparative Example 1 was measured at a frequency of 1 MHz.
  • the relative dielectric constant of each of the dielectric thin films of Examples 1 to 4 was greatly attenuated as the frequency increased to 1 MHz.
  • the relative dielectric constant of the dielectric thin film of Comparative Example 1 did not greatly attenuate even when the frequency was increased to 1 MHz.
  • the relative dielectric constant of the dielectric thin film of Comparative Example 1 was larger than the relative dielectric constant of each of the dielectric thin films of Examples 1 to 4.
  • Comparative Example 1 formed at a partial pressure of oxygen of 10 Pa showed a pattern having a peak 21 very similar to the peak of SrTaO 2 N having a perovskite structure.
  • Examples 1 to 3 in which a film was formed at an oxygen partial pressure of 0.01 to 1 Pa showed a pattern having a peak different from the peak of SrTaO 2 N having a perovskite structure.
  • the peak common to only Examples 1 to 3 was shifted to a higher angle side as the oxygen partial pressure during film formation was smaller. That is, the smaller the oxygen partial pressure during film formation, the smaller the crystal lattice contained in the dielectric thin film. It is considered that the reason why the crystal lattice included in a dielectric thin film having a lower oxygen partial pressure during film formation becomes smaller is that the number of O defects caused by insufficient O during film formation increases. It is considered that the lower the oxygen partial pressure during film formation, the more the radicalized nitrogen is forcibly introduced into the smaller crystal lattice, so that the crystal strain in the obtained dielectric thin film increases and the relative dielectric constant increases. Can be
  • Example 5 to 7 Example 5 to 7 were carried out under the same conditions as in Example 2 except that the irradiation time of the radical nitridation was increased. Table 3 shows the results.
  • the relative dielectric constant of each of the dielectric thin films of Examples 5 to 7 and Comparative Example 1 was measured at a frequency of 1 MHz.
  • the relative dielectric constant of each of the dielectric thin films of Examples 5 to 7 was greatly attenuated as the frequency increased to 1 MHz.
  • the relative dielectric constant of the dielectric thin film of Comparative Example 1 did not greatly attenuate even when the frequency was increased to 1 MHz.
  • the dielectric constant of the dielectric thin film of Comparative Example 1 was larger than the dielectric constant of each of the dielectric thin films of Examples 5 to 7.
  • Example 8 shows the same tendency even when the type of the film-forming target was changed. Note that the crystal structure of the dielectric thin film of Example 8 was a perovskite structure different from the crystal structures of the dielectric thin films of the other examples. The dielectric thin film of Example 8 had good relative dielectric constant and tan ⁇ .
  • the relative dielectric constant of each of the dielectric thin films of Examples 8 to 9 and Comparative Example 1 was measured at a frequency of 1 MHz.
  • the relative dielectric constant of each of the dielectric thin films of Examples 8 and 9 was greatly attenuated as the frequency increased to 1 MHz.
  • the relative dielectric constant of the dielectric thin film of Comparative Example 1 did not greatly attenuate even when the frequency was increased to 1 MHz.
  • the relative dielectric constant of the dielectric thin film of Comparative Example 1 was larger than the relative dielectric constant of each of the dielectric thin films of Examples 8 and 9.

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Abstract

Le problème de la présente invention est de fournir un élément capacitif et une couche mince diélectrique ayant une faible perte diélectrique et une grande constante diélectrique, particulièrement à des fréquences faibles. La solution de l'invention porte sur une couche mince diélectrique comprenant un oxynitrure A-B-O-N. Quand l'oxynitrure est représenté par la formule de composition AaBbOoNn, (o + n)/a < 3,00 est satisfait.
PCT/JP2019/033545 2018-08-31 2019-08-27 Couche mince diélectrique, élément capacitif, et substrat de circuit électronique WO2020045447A1 (fr)

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WO2017135296A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Film mince diélectrique polycristallin et élément capacitif
WO2017135298A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Composition de porcelaine diélectrique et composant électronique
WO2017135294A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Film diélectrique mince polycristallin et élément condensateur

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KR100691437B1 (ko) 2005-11-02 2007-03-09 삼성전기주식회사 폴리머-세라믹의 유전체 조성물, 이를 이용하는 내장형캐패시터와 인쇄회로기판
JP6296207B2 (ja) * 2015-10-02 2018-03-20 Tdk株式会社 誘電体薄膜、容量素子および電子部品

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Publication number Priority date Publication date Assignee Title
WO2017135296A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Film mince diélectrique polycristallin et élément capacitif
WO2017135298A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Composition de porcelaine diélectrique et composant électronique
WO2017135294A1 (fr) * 2016-02-01 2017-08-10 Tdk株式会社 Film diélectrique mince polycristallin et élément condensateur

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